New monoazodyestuffs



Patented May 10, 1932 UNITED STATE-S PATENT .oFjFQICE' I WIIN'FRID HENTRIGH, or ERLANGEN, KARL BURR AND HUGO scnwnxrznn, or LEVER- KUSEN-WIESDORF, GERMANY, ASSIGNORS '10 GENERALIANILINE wonxs, me, or I new YORK, n.1, A CORPORATION or DELAWARE I I NEW MoN'oAzonYEstrU 'Fs nbnr'awin Application filed May 28, 1931, Serial No. 540,812, and in Germany June 7, i930.

. The present invention relatestonew monoazodyestufl's, more particularly it relates to dyestuffs which may be represented by the general formula: I

B1\N/Blk0-VSO3H group,,but 3 and 2 not simultaneously'representing a hydroxy group and a carboxylic acid group, and wherein the'benzene nucleus R may be substituted by halogen, alkyl, alkoxy; the nitro group, theamino group and I i :the acylamino group. r I, I I I Our new dyestufi'sare obtainable by diazotizing in the'usual manner an amine of the general formula:

whereinthe figures meanthe same as stated above, and coupling in an acid medium with a coupling component of the general formula:

wherein any and z are to be defined as in thej first general formula. 1

Amines of the type referred-t0 above com-I '-ing into consideration as diazotization com-E ponents for the purpose of our'in'vention'are for example!" I I NHI I I I oneom-o-som som I om-onro-sona I I som NH-CO- OH;

I OHr-CHrO-S 0 1H O H: i

The said compounds can be obtained by causing 1 the corresponding 1-aminobenzene-2- sulfoxalkylarylides to react with sulfuric acid (for example 01360 or 66 Be.) at ordinary or' moderately elevated temperature. They can be isolated as Well crystallized sodium salts and diazotized in the customary manner in aqueous solution, whereby readily crystal-t lizing, stable diazocompounds areproduced.

When the diazotization of the amino aryl sulfoxalkyl'arylides is carried'out in 'sulfonic acid of the above concentration by means of nitrosyl sulfuri'cacidan esterification of the aliphatic hydroxyl group proceeds simul r taneously with the diazotizationl I Our-new dyestuffs are in form of their alkali metal salts generally bluish-red to bluish-black powders, soluble in Water and.

dyeing wool from anacid bath bluish-red to blue shades of good fastness properties.

The invention is illustrated by the following examples without being limited thereto:

Example 1.4:3.9 parts by weight of 4- nitro-l-amino-benzene-Q-sulfanilide N oxethyl sulfuric acid ester (sodium salt) are diazotized in aqueous solution and the diazo solution is combined with a solution of 23.7 parts by weight of Q-methyIami'nO-naphthalene-7-sulfonic acid maintained Weakly acid to Congo. The resulting dyestufi' having in itsfree state the following formula: V

dyes wool from an acid bath in clear reddishblue shades and possess besides; other satis; factory fastness properties a very good solubility. 7

Dyestuffs or similar'p'ropertie's but of redder shades are obtained by combining the same diazo solution with 2-naphthylamine-6- sulfonic acid, or Q-naphthylamine-TZ:sulfonic act ' solubility.

acid. .7

E wample ifBycombining the diazo solution of the amine described in Example 1 with a solutionof 23.9 parts by weight of 2- amino-S-hydroxynaphthalene-6-sulfonic acid 7 maintained weakly acid to Congo a marine blue wool dyestuff having ini'ts free state the following formula:

of very good solubility and-fastness properties results.

A wool dyestuff of similar good properties but of a somewhat greener shade is produced when the diazo compound of the samelamine isolated by salti ng out and filtering is comb-ined in an acid'medium with .3 partsby weight of 2-methylamino-8-hydr.oxynaphthalene fi-sulfonic acid-L A bluish green dyestufi is obtainedby replacing l-nitro-l-ami nobenzene s2 sulfa-nilide N-oxethylsulfuricacid ester by the I l-nitro-l aminobenzene-2- sulfo 2" anisi'dide-N oxethyl sulfuric acid ester, whilethe corresponding 2- and eV-tolu-idideor chloroanili'de sulfuric acid esters yield quite similar shadesto the a'n'i lide sul' furic acid esteri By coupling the sulfuric acid ester of l-nitro-1-aminobenzeneQ sulfoxal kyl aryli'des with 2-methylaminonaph-' thalene-7-sulfonic acid, acid dyestuffs are obtained which dye animal fibres in fast marine blue shades and which possess very good obtained as according to the method given in Example 1. a c s The 2-anisidide," Q toIuidide; P-toluidide, 2'-'chloroa'nilide, and4-ch1or0ani1ide of l-nitro-l-aminobenzene-Q-sulfonic acid substituted by oxethyl in the sO NH-group are prepared by the action of;4=-nitro-1'-chlorobenzene-2 -sulfochloride on oxethyl-o-anisidine,- ox ethyl o toluidine, oxethyl p-toluidine', oxethyl-o-chlor'nani-line, oxethyl-pmhld roaniline' and replacing the chlorine inthe'l position by an amino groupby meansof ammonia under pressure; The: substituted oxethylanilides are prepared from the corresponding primary amines 'by the action of glycol-chlorohydrine by heating in water and in the presence, of an'ja cid binding agent.

E mamp-Ze 3.A65.6 "parts by weight of the sodium salt of the *dyesttifl' of Example 2 obtained by coupling in'an acid medium diazotized l-nitro-l-aminobenzene-2 sulfanilide- N-'oxethylsulfurici acid esterrvith 2-amino 8''-hydroxynaphthalene-6 sulfonic acid are dissolved in'5001part's by wei ht of water at a To the solutemperature of about tion' there are" added sapms by weight'of an aqueous sodium sulfide solution (one liter cumming-1000 g; of crystallized sodium sulfide ).-,-the solution is kept at'thistemperature for a short time, boiled up, purified'by filter; ing and the dyestufl is'sal'ted out by means of common salt. In'itsfree state the dyestnfi has the following formula:

' N N on I V HO S-O-OHrOHg-N-SO nm 7 p aH-ax 4 SOaH In quite an analogous manner thedyestufis further mentioned in Example 2 may be reduced. i

By acetylating the amino group in the benzene nucleus dyestufi's are obtained from these compounds some of which exhibit still better properties, the shadebeing displaced further towards red, 1

- Thesame dyestufis are produced by combinin'g in an acid medium the 'dia'zo solution from, i-acetylamino-l-aminobenzene-2;sulf= arylide-N-oxethyl sulfuricfacid ester'with 2 amino- 8' -hydroxynaphthalene fi-sulfonie' acid or 2-methylamino-8-hydroxynaphthalene-G-sulfonic acid. Furthermore dyestufl's of identical fastness properties and very good solubility are obtained by combining the same diazo compound with Q-methylamino-naphthalene-7-sulfonic acid, 2-naphthylamine-6- sulfonic acid or 2-naphthylamine-7-sulfonic acid.

We claim:

1. As new products azodyestufls of the probable general formula:

wherein R stands for a benzene nucleus which may be substituted by halogen, alkyl or alkoxy, alk stands for an alkylene group, 00 stands for hydrogen, alkyl or phenyl, y stands for hydrogen or a hydroxy group, 2 stands for a sulfonic acid group or a carboxylic acid group, but 3 and a not simultaneously representing a hydroxy group and a carboxylic acid group, and wherein the benzene nucleus R may be substituted by halogen, alkyl, alkoxy, the nitro group, the amino group and the acylamino group, being in the form of their alkali metal salts generally bluish-red to bluish-black powders, soluble in water and dyeing wool from an acid bath bluish-red to blue shades of good fastness properties.

2. As new products azodyestufi's of the probable general formula:

' SOaH wherein R stands for a benzene nucleus which may be substituted by halogen, alkyl or alkoxy, alk stands for an alkylene group, :20 stands for hydrogen, methyl or ethyl, 3 stands for hydrogen or a hydroxy group,

and wherein the benzene nucleus R may be substituted by halogen, alkyl, alkoxy, the nitro group, the amino group and the acylamino group, being in the form of their alkali metal salts generally bluish-red to bluishblack powders, soluble in water and dyeing wool from an acid bath bluish-red to blue shades of good fastness properties.

drogen or a hydroxy 3. As new products azodyestufis of the probable general formula: I

l 503K I V wherein alk stands for an alkylene group containing two carbon atoms, 8 stands for a nitro, amino or acylamino group,w stands for hydrogen, methyl or ethyl, y stands for hygroup, being in the form of their alkali metal salts generally bluish-red to bluish-black powders, soluble in water and dyeing wool from an acid bath bluish-red to-blue shades of good fastness properties. j

4. As a new product the azodyestufi of the following formula:

NO: dyeing wool from an acid bath in clear reddish-blue shades of good fastness properties. 1

5; As a new product the azodyestufl of the following formula:

N=N O H HzN i i 7 N =N OH HOaS-O-OHa-N-SO HIN dyeing wool from an acid bath reddish-blue shades of good fastness properties.

In testimony whereof, we aflix our signatures.

. KARL BURR.

HUGO SGHWEITZEB.

AWINFRID HEN-THIGH. 

